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WO2012157413A1 - Dénitrateur et procédé de dénitration - Google Patents

Dénitrateur et procédé de dénitration Download PDF

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Publication number
WO2012157413A1
WO2012157413A1 PCT/JP2012/060986 JP2012060986W WO2012157413A1 WO 2012157413 A1 WO2012157413 A1 WO 2012157413A1 JP 2012060986 W JP2012060986 W JP 2012060986W WO 2012157413 A1 WO2012157413 A1 WO 2012157413A1
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WO
WIPO (PCT)
Prior art keywords
denitration
correlation
catalyst
nox concentration
reducing agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/060986
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English (en)
Japanese (ja)
Inventor
松山　直樹
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Sumitomo Heavy Industries Ltd
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Sumitomo Heavy Industries Ltd
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Publication date
Application filed by Sumitomo Heavy Industries Ltd filed Critical Sumitomo Heavy Industries Ltd
Priority to KR1020137027020A priority Critical patent/KR101470784B1/ko
Priority to PH1/2013/502346A priority patent/PH12013502346A1/en
Publication of WO2012157413A1 publication Critical patent/WO2012157413A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8631—Processes characterised by a specific device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8696—Controlling the catalytic process
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/006—Layout of treatment plant
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23N—REGULATING OR CONTROLLING COMBUSTION
    • F23N5/00—Systems for controlling combustion
    • F23N5/003—Systems for controlling combustion using detectors sensitive to combustion gas properties
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/10—Nitrogen; Compounds thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2219/00—Treatment devices
    • F23J2219/10—Catalytic reduction devices
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2219/00—Treatment devices
    • F23J2219/20—Non-catalytic reduction devices

Definitions

  • the present invention relates to a denitration apparatus and a denitration method.
  • a denitration device described in Patent Document 1 below is known as a denitration device that removes (denitration) nitrogen oxides (NOx) contained in exhaust gas from a combustion furnace.
  • ammonia reducing agent
  • this denitration apparatus ammonia (reducing agent) is injected into combustion exhaust gas from a pressurized fluidized bed boiler that is a combustion furnace to perform non-catalytic denitration to obtain reduced treatment exhaust gas, and further ammonia is injected into this reduced treatment exhaust gas, Catalyst denitration is performed by a denitration catalyst device having a denitration catalyst to obtain catalyst-passing exhaust gas, and the catalyst-passing exhaust gas is discharged from the chimney to the outside.
  • a control function that correlates the operating load of the pressurized fluidized bed boiler with the ammonia injection amount necessary for removing NOx contained in the exhaust gas from the pressurized fluidized bed boiler at the time of this operating load is controlled by ammonia injection.
  • the ammonia injection control means receives the load signal from the pressurized fluidized bed boiler and controls the ammonia injection amount based on the control function described above.
  • the circulating fluidized bed boiler is more effective in exhaust gas than other types of boilers. Since the amount of soot contained in the catalyst is large, the soot may be clogged with the catalyst used for the catalytic denitration and the catalyst may be deteriorated.
  • circulating fluidized bed boilers may burn fuels such as biomass, waste plastic, waste tires, sludge, RPF (Refuse Paper & Plastic Fuel), and RDF (Refuse Derived Fuel). Although possible, these fuels contain heavy metals such as lead and zinc, sodium, potassium, phosphorus, etc., and these substances may deteriorate the catalyst.
  • the ammonia injection amount is set using a control function that correlates the boiler load and the ammonia injection amount as in the above-described denitration device. Even if controlled, NOx cannot be sufficiently removed as desired.
  • the present invention has been made to solve such problems, and provides a denitration apparatus and a denitration method that can sufficiently remove NOx even if a catalyst used for catalytic denitration deteriorates. Objective.
  • a denitration apparatus includes a non-catalytic denitration means for performing non-catalytic denitration by injecting a reducing agent into exhaust gas containing NOx generated in a combustion furnace, and a reductant for the exhaust gas subjected to non-catalytic denitration.
  • a denitration apparatus comprising a catalytic denitration means for injecting and performing catalytic denitration using a denitration catalyst, the correlation between the load of the combustion furnace and the amount of reducing agent injected by the noncatalytic denitration means One correlation is stored in advance, the amount of reducing agent injected by the non-catalytic denitration means is controlled based on the first correlation, and the inlet is the NOx concentration at the combustion furnace load and the denitration catalyst inlet side.
  • the second correlation which is a correlation with the NOx concentration is stored in advance, the inlet NOx concentration is predicted based on the second correlation, and the reducing agent injection amount injected by the catalytic denitration means based on the inlet NOx concentration
  • control means for controlling NOx removal catalyst A catalyst deterioration detecting means for detecting deterioration, and the control means rewrites the first correlation and the second correlation according to the deterioration of the denitration catalyst when the catalyst deterioration detection means detects that the denitration catalyst has deteriorated. It is possible to do this.
  • the denitration method performs non-catalytic denitration by injecting a reducing agent into exhaust gas containing NOx generated in a combustion furnace, and injects the reducing agent into the exhaust gas subjected to non-catalytic denitration,
  • a denitration method for performing catalytic denitration using a denitration catalyst wherein a first correlation that is a correlation between a load of a combustion furnace and an injection amount of a reducing agent injected by non-catalytic denitration is stored in advance, and a first correlation Based on the relationship, the amount of reducing agent injected by non-catalytic denitration is controlled, and the second correlation is a correlation between the load of the combustion furnace and the NOx concentration at the inlet side of the denitration catalyst Is stored in advance, the inlet NOx concentration is predicted based on the second correlation, the injection amount of the reducing agent injected by catalytic denitration is controlled based on the inlet NOx concentration, and it is detected that the
  • the load of the combustion furnace and the amount of reducing agent injected by non-catalytic denitration are stored in advance as a first correlation, and the amount of reducing agent injected by non-catalytic denitration means is controlled according to the load of the combustion furnace. Is done. Also, the load of the combustion furnace and the inlet NOx concentration are stored in advance as a second correlation, the inlet NOx concentration is predicted from the load of the combustion furnace, and the amount of reducing agent injected by catalytic denitration according to the inlet NOx concentration Is controlled.
  • the first correlation and the second correlation can be rewritten according to the deterioration of the denitration catalyst to optimally adjust the reducing agent injection amount. Even if the catalyst used in the process deteriorates, NOx can be sufficiently removed.
  • control means may be capable of storing a plurality of first correlations and second correlations according to the type of fuel combusted in the combustion furnace. In this way, the amount of reducing agent injected can be adjusted more optimally according to the type of fuel combusted in the combustion furnace.
  • the present invention it is possible to provide a denitration apparatus and a denitration method that can sufficiently remove NOx even if a catalyst used for catalytic denitration deteriorates.
  • FIG. 1 It is a block diagram which shows the denitration apparatus to which the denitration method which concerns on embodiment of this invention is applied. It is a graph which shows the 1st correlation. It is a graph which shows a 2nd correlation. It is a flowchart which shows operation
  • FIG. 1 is a configuration diagram showing a denitration apparatus to which a denitration method according to an embodiment of the present invention is applied.
  • a denitration apparatus 100 is provided in a plant P including a boiler (combustion furnace) 1 that is a circulating fluidized bed boiler here, and nitrogen oxide (NOx) contained in exhaust gas from the boiler 1. ).
  • a boiler combustion furnace
  • NOx nitrogen oxide
  • the plant P In the plant P, first, in the boiler 1, in addition to fossil fuels such as coal, fuels such as biomass, waste plastics, waste tires, sludge, RPF, and RDF are mixed with the air supplied into the boiler 1.
  • the exhaust gas is combusted while circulating in the boiler 1, and exhaust gas containing solid particles such as dust and NOx is generated by this combustion, and the exhaust gas is sent to the cyclone 2 from the first duct D 1 connected to the upper part of the boiler 1. .
  • solid particles are separated from the exhaust gas by solid-gas separation by centrifugal separation, and the solid particles separated from the exhaust gas are returned to the boiler 1 through a pipe from the bottom of the cyclone 2, while the solid particles are separated.
  • the exhaust gas is sent from the upper part of the cyclone 2 to the heat recovery units 3 and 4 through a pipe.
  • heat is recovered from the exhaust gas, and the exhaust gas after the heat recovery is sent to the exhaust gas purification device 5 through the second duct D2.
  • the exhaust gas purification device 5 fine solid particles such as fly ash still entrained in the exhaust gas are removed and the exhaust gas is desulfurized to purify the exhaust gas, and the purified exhaust gas is discharged to the outside through the chimney 6. Is done.
  • a denitration apparatus 100 provided in such a plant P includes a first NH 3 (ammonia) injection unit 7, a second NH 3 injection unit 8, a denitration catalyst installation unit 9, a catalyst inlet O 2 concentration meter 10, and a catalyst inlet NOx concentration meter 11.
  • the first NH 3 injection unit 7 functions as non-catalytic denitration means for performing non-catalytic denitration by injecting a reducing agent (here, NH 3 ) into exhaust gas containing NOx generated in the boiler 1. and it is provided so as to inject NH 3 to the first duct D1 between the cyclone 2.
  • a reducing agent here, NH 3
  • Non-catalytic denitration is performed, for example, in a region where the temperature of exhaust gas is about 700 to 1100 ° C.
  • the 2NH 3 injection unit 8 is adapted to inject NH 3 in the exhaust gas was carried out without a catalyst denitration in the first duct D1, it is provided so as to inject NH 3 between the heat recovery unit 3,4 . Further, the denitration catalyst installation section 9, the exhaust gas of ammonia from the 2NH 3 injection unit 8 is injected is for removing NOx by passing the installation the denitration catalyst, a 2NH 3 injection unit 8 and the heat It arrange
  • the denitration catalyst for example, a ceramic having vanadium supported thereon is used.
  • the catalyst surface area S (m 2 ), which is the surface area of the denitration catalyst is a fixed value determined by the operating conditions of the plant P, and is stored in advance in the catalyst deterioration detection unit 16.
  • the catalytic denitration is performed, for example, in a region where the temperature of the exhaust gas is about 200 to 400 ° C.
  • the pipe connecting the second 1N H 3 injection unit 7 and the NH 3 supply unit 19, a 1N H 3 injection rate is the amount of NH 3 to be supplied to the 1N H 3 injection section 7 A in1 the (Nm 3 / h) and the 1N H 3 flow meter 20 for measuring a first control valve 21 for adjusting the amount of NH 3 to be supplied to the 1N H 3 injection section 7 is provided.
  • a second NH 3 injection amount A in2 (Nm 3 / h), which is the amount of NH 3 supplied to the second NH 3 injection part 8, is used.
  • a second NH 3 flow meter 22 to be measured and a second control valve 23 for adjusting the amount of NH 3 supplied to the second NH 3 injection section 8 are provided.
  • the catalyst inlet O 2 concentration meter 10 is disposed between the second NH 3 injection section 8 and the denitration catalyst installation section 9, and has an inlet O 2 concentration that is the concentration of O 2 in the exhaust gas on the inlet side of the denitration catalyst installation section 9. B in (%) is measured.
  • the catalyst inlet O 2 concentration meter 10 is connected to the catalyst deterioration detector 16 and outputs the measured inlet O 2 concentration B in to the catalyst deterioration detector 16.
  • the catalyst inlet NOx concentration meter 11 is disposed between the second NH 3 injection section 8 and the denitration catalyst installation section 9, and has an inlet NOx concentration C in (the concentration of NOx in the exhaust gas on the inlet side of the denitration catalyst installation section 9. ppm).
  • the catalyst inlet NOx concentration meter 11 is connected to the catalyst deterioration detector 16 and outputs the measured inlet NOx concentration C in to the catalyst deterioration detector 16.
  • the catalyst inlet O 2 concentration meter 10 and the catalyst inlet NOx concentration meter 11 disposed on the inlet side of the denitration catalyst installation unit 9 are deteriorated by fine solid particles such as fly ash still accompanying the exhaust gas. It is preferable to operate intermittently because there is a risk of causing problems. Therefore, in this embodiment, the catalyst inlet O 2 concentration meter 10 and the catalyst inlet NOx concentration meter 11 operate only when the catalyst deterioration detector 16 described later in detail determines deterioration of the denitration catalyst, and during other operations. It doesn't work.
  • the catalyst outlet O 2 concentration meter 12 is disposed in the second duct D2, and measures the outlet O 2 concentration B out (%), which is the concentration of O 2 in the exhaust gas on the outlet side of the denitration catalyst installation unit 9. .
  • the catalyst outlet O 2 concentration meter 12 is connected to the catalyst deterioration detection unit 16, and outputs the measured outlet O 2 concentration B out to the catalyst deterioration detection unit 16.
  • the catalyst outlet NOx concentration meter 13 is disposed in the second duct D2 and measures the outlet NOx concentration C out (ppm), which is the concentration of NOx in the exhaust gas on the outlet side of the denitration catalyst installation unit 9.
  • the catalyst outlet NOx concentration meter 13 is connected to the catalyst deterioration detection unit 16 and outputs the measured outlet NOx concentration C out to the catalyst deterioration detection unit 16.
  • the catalyst outlet NOx concentration meter 13 is connected to the denitration distribution unit 18 and outputs the measured outlet NOx concentration Cout to the denitration distribution unit 18.
  • the catalyst outlet NH 3 concentration meter 14 is disposed in the second duct D2 and measures the outlet NH 3 concentration A out (ppm), which is the concentration of NH 3 in the exhaust gas on the outlet side of the denitration catalyst installation unit 9. .
  • the catalyst outlet NH 3 concentration meter 14 is connected to the catalyst deterioration detection unit 16, and outputs the measured outlet NH 3 concentration A out to the catalyst deterioration detection unit 16.
  • the exhaust gas flow rate calculation unit 15 calculates an exhaust gas amount G (Nm 3 / h) that is a flow rate of exhaust gas that passes through the first duct D1, and is connected to the catalyst deterioration detection unit 16, and calculates the calculated exhaust gas amount G. Output to the catalyst deterioration detector 16.
  • the exhaust gas flow rate calculation unit 15 calculates the exhaust gas amount G by installing a flow meter in the first duct D1 and using a value measured by the flow meter, and calculating from the load of the boiler 1 And a method of calculating from the amount of fuel combusted in the boiler 1 are used.
  • the catalyst deterioration detection unit 16 functions as a catalyst deterioration detection unit that detects whether or not the denitration catalyst has deteriorated more than a predetermined level, and includes a CPU (Central Processing Unit), a ROM (Read Only Memory), and a RAM (Random). It is composed of an electronic control unit composed of (Access Memory).
  • the catalyst deterioration detection unit 16 calculates a reaction rate constant K expressed by the following formula (1) using various input values. Then, the catalyst deterioration detection unit 16 determines whether or not the denitration catalyst has deteriorated more than a predetermined value by determining whether or not the reaction rate constant K is below a predetermined threshold value stored in advance. Detects catalyst deterioration.
  • AV (Nm / h) represents the area velocity
  • Eff represents the denitration efficiency
  • ⁇ represents the molar ratio
  • C in6%, C out6% , A out6% , using B in and B out is the oxygen concentration in the inlet and outlet sides of the denitration catalyst installation section 9, the same oxygen concentration under (6% in this case) It is the value converted into the concentration at.
  • the catalyst deterioration detection unit 16 is connected to the denitration distribution unit 18 and outputs a signal to that effect to the denitration distribution unit 18 when it is detected that the denitration catalyst has deteriorated more than a predetermined level.
  • the boiler operation unit 17 is for controlling the operation of the boiler 1, and is configured by an electronic control unit in the same manner as the catalyst deterioration detection unit 16.
  • the boiler operation unit 17 is connected to the denitration distribution unit 18 and outputs information such as the load on the boiler 1 and the type of fuel combusted in the boiler 1 to the denitration distribution unit 18.
  • the load on the boiler 1 can be determined from the amount of fuel combusted in the boiler 1, for example.
  • Denitration distributor 18 which functions as a control means for controlling determines the amount of NH 3 supplied from the NH 3 supply unit 19 to the 1N H 3 injection section 7 and the 2NH 3 injection unit 8, the catalyst deterioration detection As with the section 16, it is composed of an electronic control unit.
  • FIG. 2 is a graph showing the first correlation
  • FIG. 3 is a graph showing the second correlation
  • Denitration distributor 18, as shown in FIG. 2 stores a graph showing a first correlation is a correlation between the load of the boiler 1 3 injection rate (horizontal axis) and the 1N H A in1 (vertical axis) Yes.
  • a plurality of graphs showing the first correlation are stored according to the degree of deterioration of the denitration catalyst and the type of fuel combusted in the boiler 1.
  • the denitration distribution unit 18 injects the first NH 3 injection based on the load information of the boiler 1 input from the boiler operation unit 17 according to the degree of deterioration of the denitration catalyst and the type of fuel combusted in the boiler 1.
  • the first NH 3 injection amount A in1 supplied to the unit 7 is determined (details will be described later).
  • the concentration of NOx remaining in exhaust gas was carried out without a catalyst denitration (inlet NOx concentration C in)
  • inlet NOx concentration C in the concentration of NOx remaining in exhaust gas was carried out without a catalyst denitration
  • the denitration distributor 18 in order to predict the inlet NOx concentration C in, a correlation between, as shown in FIG. 3, of the boiler 1 load (horizontal axis) and the inlet NOx concentration C in (ordinate) first 2 A graph showing the correlation is stored.
  • the graph indicating the second correlation can be created, for example, from the measurement result during the trial operation of the plant P. Further, a plurality of graphs indicating the second correlation are stored according to the degree of deterioration of the denitration catalyst and the type of fuel combusted in the boiler 1, corresponding to the graph indicating the first correlation.
  • the denitration distribution unit 18 determines the inlet NOx concentration C based on the load information of the boiler 1 input from the boiler operation unit 17 according to the degree of deterioration of the denitration catalyst and the type of fuel combusted in the boiler 1. to predict the in (the details will be described below).
  • the denitration distribution unit 18 determines the second NH 3 injection amount A in2 by the following equation (2) based on the inlet NOx concentration C in predicted from the second correlation.
  • C target represents the NOx removal target NOx concentration (ppm), which is the target NOx concentration after catalytic denitration.
  • the denitration distribution unit 18 includes a graph for determining the first NH 3 injection amount A in1 when the signal indicating that the denitration catalyst installation unit 9 has deteriorated more than a predetermined value is input from the catalyst deterioration detection unit 16, and the inlet It is possible to rewrite the graph for predicting the NOx concentration C in to another stored graph (details will be described later).
  • the denitration distribution unit 18 is provided with a manual switch (not shown). When this manual switch is pressed, the denitration distribution unit 18 sets the first NH 3 injection amount A in1 even when the signal indicating that the denitration catalyst installation unit 9 has deteriorated more than a predetermined value is not input from the catalyst deterioration detection unit 16. It is possible to forcibly rewrite the graph for determination and the graph for predicting the inlet NOx concentration C in to another stored graph.
  • the manual switch is pushed, for example, when the second NH 3 injection amount A in2 in the catalytic denitration is not obtained as desired due to a problem such as clogging of the second NH 3 injection portion 8, forcibly, For example, the second NH 3 injection amount A in2 in the catalytic denitration is decreased, and instead the first NH 3 injection amount A in1 in the non-catalytic denitration is increased.
  • the sampling inspection of the denitration catalyst installation unit 9 is performed, and when it is determined that the denitration catalyst is deteriorated, the catalyst is forcibly
  • the second NH 3 injection amount A in2 in the denitration is decreased, and instead the first NH 3 injection amount A in1 in the non-catalytic denitration is increased.
  • the denitration distributor 18 is connected to the first control valve 21 and sends a control signal (a) to the first control valve 21 so that the determined first NH 3 injection amount A in1 is obtained. Further, the denitration distributor 18 is connected to the second control valve 23 and sends a control signal (b) to the second control valve 23 so that the determined second NH 3 injection amount A in2 is obtained.
  • denitration distributor 18 the outlet NOx concentration C out input from catalyst outlet NOx concentration meter 13, and checks whether the desired denitration performance is exhibited, it is possible to perform the feedback control Yes.
  • FIG. 4 is a flowchart showing the operation of the denitration apparatus shown in FIG.
  • the operation of the denitration apparatus 100 is such that the denitration distribution unit 18 determines whether or not a signal indicating that the denitration catalyst has deteriorated more than a predetermined value is input from the catalyst deterioration detection unit 16. It starts from executing the determination (step S101). Whether or not the denitration catalyst has deteriorated more than a predetermined value is determined by the catalyst deterioration detection unit 16 calculating a reaction rate constant K and determining whether or not the reaction rate constant K is below a predetermined threshold value stored in advance. Judge by. The determination by the catalyst deterioration detection unit 16 is performed at a predetermined interval, for example, once a day, and is not performed during other operations.
  • step S101 When it is determined in step S101 that no signal is input, the denitration distribution unit 18 performs manual determination of catalyst deterioration progress to determine whether or not the manual switch has been pressed (step S103).
  • step S103 if it is determined that it has not been pressed manual switch, the denitration distributor 18, the amount of NH 3 supplied from the NH 3 supply unit 19 to the 1N H 3 injection section 7 and the 2NH 3 injector 8 It is determined that the denitration distribution adjustment for adjusting the NO is unnecessary, and the series of operations of the denitration apparatus 100 ends.
  • step S101 determines that a signal has been input, or if it is determined in step S103 that the manual switch has been pressed.
  • step S105 determines that denitration distribution adjustment is necessary.
  • the denitration efficiency in the catalytic denitration is high. Therefore, in order to actively perform the catalytic denitration, the first NH 3 injection amount A in1 in the non-catalytic denitration is decreased, It is preferable to increase the second NH 3 injection amount A in2 . Therefore, denitration distributor 18, as shown in FIG. 2 (a), by selecting the graph first 1N H 3 injection amount A in1 is small to determine a second 1N H 3 injection amount A in1, a 1N H 3 injection determined the amount a in1 accordance together with transmission control signal (a) to the first control valve 21 to inject NH 3 from the 1N H 3 injection unit 7, as shown in FIG.
  • a high inlet NOx concentration C in The graph is selected to predict the inlet NOx concentration C in
  • the second NH 3 injection amount A in2 is determined based on the above equation (2)
  • the second control valve is determined according to the determined second NH 3 injection amount A in2
  • a control signal (b) is transmitted to 23 and NH 3 is injected from the second NH 3 injection section 8.
  • the denitration efficiency in the catalytic denitration is lowered. Therefore, the first NH 3 injection amount A in1 in the noncatalytic denitration is also used in order to use noncatalytic denitration. Is increased, and the amount of second NH 3 injection A in2 in catalytic denitration is preferably reduced.
  • the denitration distribution unit 18 next displays a graph for determining the first NH 3 injection amount A in1 in accordance with the deterioration of the denitration catalyst, as shown in FIG. As shown in b) and (c), a graph for predicting the inlet NOx concentration C in corresponding to this is rewritten step by step to a graph with a large first NH 3 injection amount A in1 (step S107). , FIG. 3 (b), the (c), the stepwise rewritten inlet NOx concentration C in the lower graph (step S109).
  • the series of operations of the denitration apparatus 100 is terminated, and the 1N H 3 injection amount A in1, which is determined based on the rewritten graph, pursuant 2NH 3 injection amount A in2 and a 1N H 3 injection section 7, NH 3 is injected from the second NH 3 injection section 8.
  • the load of the boiler 1 and the first NH 3 injection amount A in1 that is the amount of NH 3 injected by non-catalytic denitration are as a first correlation, the denitration distribution unit.
  • the first NH 3 injection amount A in1 is controlled according to the load of the boiler 1.
  • the load of the boiler 1, and the inlet NOx concentration C in the concentration of NOx in the exhaust gas at the inlet side of the denitration catalyst installation portion 9, stored in advance in the denitration distribution portion 18 as a second correlation the boiler 1 inlet NOx concentration C in is predicted according to the load
  • the 2NH 3 injection amount a in2 is the amount of NH 3 to be injected in organic catalyst denitration is controlled according to the inlet NOx concentration C in.
  • the inlet NOx concentration Cin is predicted from the second correlation stored in advance, and therefore the catalyst inlet NOx concentration meter 11 is used for determining the deterioration of the denitration catalyst. It can be made to operate only during the other driving. Thereby, deterioration and malfunction of the catalyst inlet NOx concentration meter 11 can be suppressed.
  • the denitration distribution unit 18 stores a plurality of first correlations and second correlations according to the type of fuel combusted in the boiler 1, NH is determined according to the type of fuel combusted in the boiler 1.
  • the injection amount of 3 can be adjusted even more optimally.
  • the denitration distribution unit 18 stores the first correlation and the second correlation as a graph, but instead stores the first correlation and the second correlation as a function. May be.
  • the use of the NH 3 as a reducing agent instead of this, may be used urea water.
  • the reducing agent to be injected at the 1N H 3 injection section 7 and the 2NH 3 injection unit 8 may be the same, may be different.
  • the 1N H 3 injection section 7 is a non-catalytic denitration unit is provided in the first duct D1, may be provided in the boiler 1.
  • the 2NH 3 injector 8 and the denitration catalyst installation portion 9 is perforated catalyst denitration means is provided between the heat recovery unit 3 and 4 is not limited to this, flowing exhaust gas It suffices if it is on the downstream side of the first NH 3 injection section 7 which is a non-catalytic denitration means in the direction.
  • the present invention it is possible to provide a denitration apparatus and a denitration method that can sufficiently remove NOx even when a catalyst used for catalytic denitration deteriorates.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Treating Waste Gases (AREA)

Abstract

Cette invention concerne un dénitrateur comprenant : un moyen de dénitration non catalytique dans lequel un agent réducteur est injecté dans le gaz de carneau contenant des NOx généré dans un four à combustion, ledit gaz de carneau étant dénitré par voie non catalytique ; et un moyen de dénitration catalytique dans lequel un agent réducteur est injecté dans le gaz de carneau dénitré par voie non catalytique, ce gaz de carneau étant dénitré par voie catalytique à l'aide d'un catalyseur de dénitration. Le dénitrateur comprend en outre : un moyen de régulation qui mémorise à l'avance une première corrélation, qui est une corrélation entre la charge imposée sur le four de combustion et la quantité d'agent réducteur à injecter dans le moyen de dénitration par voie non catalytique, et régule, sur la base de la première corrélation, la quantité d'agent réducteur à injecter dans le moyen de dénitration par voie non catalytique et qui mémorise à l'avance une seconde corrélation, qui est une corrélation entre la charge imposée sur le four de combustion et la concentration d'entrée des NOx qui est la concentration des NOx mesurée côté entrée du catalyseur de dénitration, prédit la concentration d'entrée des NOx sur la base de la seconde corrélation, et régule, sur la base de la concentration d'entrée des NOx, la quantité d'agent réducteur à injecter dans le moyen de dénitration par voie catalytique ; et un moyen de détection de la détérioration du catalyseur qui détecte une détérioration du catalyseur de dénitration. Quand une détérioration du catalyseur de dénitration a été détectée par le moyen de détection de la détérioration du catalyseur, le moyen de régulation peut remplacer la première corrélation et la seconde corrélation en fonction de la détérioration du catalyseur de dénitration.
PCT/JP2012/060986 2011-05-18 2012-04-24 Dénitrateur et procédé de dénitration Ceased WO2012157413A1 (fr)

Priority Applications (2)

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KR1020137027020A KR101470784B1 (ko) 2011-05-18 2012-04-24 탈초장치 및 탈초방법
PH1/2013/502346A PH12013502346A1 (en) 2011-05-18 2012-04-24 Denitrator and denitration method

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JP2011-111472 2011-05-18
JP2011111472A JP5575701B2 (ja) 2011-05-18 2011-05-18 脱硝装置及び脱硝方法

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CN111514726B (zh) * 2019-02-02 2024-01-26 广东万引科技发展有限公司 一种新型干法水泥窑用复合生物质脱硝剂、其使用方法以及脱硝系统
CN111636934B (zh) * 2020-05-24 2021-03-16 西安交通大学 一种高效清洁高变负荷速率燃煤发电系统及运行方法
CN112651166B (zh) * 2020-11-24 2023-03-28 呼和浩特科林热电有限责任公司 脱硝系统入口氮氧化物浓度预测方法、装置及脱硝系统
CN114558434A (zh) * 2022-03-04 2022-05-31 广东瑞星环境科技有限公司 一种针对生物质锅炉烟气超净排放协同处理的方法及设备

Citations (3)

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JPH1119469A (ja) * 1997-06-30 1999-01-26 Babcock Hitachi Kk 脱硝反応器のアンモニア注入制御装置
JPH11235516A (ja) * 1998-02-24 1999-08-31 Chugoku Electric Power Co Inc:The 排ガスの脱硝装置
JP2000237536A (ja) * 1998-12-21 2000-09-05 Nkk Corp 焼却炉の排ガス脱硝装置

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JPH05103951A (ja) * 1991-10-14 1993-04-27 Ebara Corp 排ガス脱硝方法及びその装置
CA2489372C (fr) * 2002-06-14 2008-10-07 The Chugoku Electric Power Co., Inc. Dispositif de gestion du catalyseur utilise dans un dispositif d'elimination de nox et methode de gestion dudit catalyseur

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JPH1119469A (ja) * 1997-06-30 1999-01-26 Babcock Hitachi Kk 脱硝反応器のアンモニア注入制御装置
JPH11235516A (ja) * 1998-02-24 1999-08-31 Chugoku Electric Power Co Inc:The 排ガスの脱硝装置
JP2000237536A (ja) * 1998-12-21 2000-09-05 Nkk Corp 焼却炉の排ガス脱硝装置

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PH12013502346A1 (en) 2014-01-06
KR20130133291A (ko) 2013-12-06
MY165561A (en) 2018-04-05
JP5575701B2 (ja) 2014-08-20
JP2012239970A (ja) 2012-12-10

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